Composition for reducing malodor impression on inanimate surfaces

ABSTRACT

The present invention relates to an aqueous composition for reducing malodor impression. The composition comprises from about 0.01% to about 1%, by weight of the composition, of perfume wherein the perfume preferably comprises ingredients having a Clog P of 3 or smaller. Optionally, but preferably, the composition comprises from about 0.1% to about 5%, by weight of the composition of, water-soluble cyclodextrin, from about 0.1% to about 10%, by weight of the composition, of water-soluble metallic salt, from about 0% to about 3%, by weight of the composition, of solubilizing aid. The composition is essentially free of any material that would soil or stain fabric and contains less than about 5%, by weight of the composition of low molecular weight monohydric alcohols.

This is a continuation of application Ser. No. 08/289,991, filed on Aug.12, 1994, and now abandoned.

TECHNICAL FIELD

The present invention relates to aqueous, preferably clear,compositions, articles of manufacture and/or method of use, for reducingmalodor impression, comprising low levels of perfumes preferably havingperfume ingredients with a Clog P of 3 or smaller; optionally, butpreferably, water-soluble cyclodextrin; optionally, but preferably,water-soluble metallic salt; and optionally, but preferably, asolubilizing aid. Preferably, the compositions are designed to reducemalodor on inanimate surfaces, especially, clothes, e.g., those thathave been stored for a long period of time, that are contaminated withenvironmental odors such as food odors, tobacco odors, and that arewetted with perspiration. Preferably the composition is used to restoreand/or maintain freshness by reducing malodor without the need forwashing or dry cleaning.

BACKGROUND OF THE INVENTION

The present invention relates to aqueous, preferably clear,compositions, articles of manufacture, and/or method for use, as afreshening composition. Preferably, the compositions are sprayed ontofabrics, particularly clothes, to restore their freshness by reducingmalodor impression, without washing or dry cleaning. Fabrics treatedwith some preferred compositions of the present invention also releaseextra fragrance upon rewetting, such as when the wearer perspires. Thefreshening compositions of the present invention are designed to extendthe wear of fabrics between washing or dry cleaning. Fabrics treatedwith some preferred freshening compositions of the present inventionwill stay fresher longer, and receive extra freshening effect viaperfume release when it is most needed, that is upon fabric rewetting.

Odor masking is the intentional concealment of one odor by the additionof another. The preference to the masking perfume is varied greatly,depending on the application, e.g., underarm odor masking, fabric odormasking, bathroom odor masking, etc. The art teaches the use of perfumeas an odor masking device in combination with alcohol in order tosolubilize the perfume. It has now been discovered that perfumes with aClog P of less than 3 do not need alcohol in order to be solubilized.

SUMMARY OF THE INVENTION

The present invention relates to an aqueous composition for reducingmalodor impression, comprising:

(A) from about 0.01% to about 1%, by weight of the composition, ofperfume wherein the perfume preferably comprises ingredients having aClog P of 3 or smaller;

(B) optionally, but preferably, from about 0.1% to about 5%, by weightof the composition of, water-soluble cyclodextrin;

(C) optionally, but preferably, from about 0.1% to about 10%, by weightof the composition, of water-soluble metallic salt;

(D) optionally, but preferably, from about 0% to about 3%, by weight ofthe composition, of solubilizing aid; and

(E) aqueous carrier; and

wherein said composition is essentially free of any material that wouldsoil or stain fabric and wherein said composition contains less thanabout 5%, by weight of the composition of low molecular weightmonohydric alcohols.

The composition can be incorporated into a spray dispenser to create anarticle of manufacture that can facilitate treatment of articles and/orsurfaces with the composition to reduce malodor at a level that iseffective, yet is not discernible when dried on the surface.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an aqueous composition for reducingmalodor impression, comprising:

(A) from about 0.01% to about 1%, by weight of the composition, ofperfume wherein the perfume preferably comprises ingredients having aClog P of 3 or smaller;

(B) optionally, but preferably, from about 0.1% to about 5%, by weightof the composition of, water-soluble cyclodextrin;

(C) optionally, but preferably, from about 0.1% to about 10%, by weightof the composition, of water-soluble metallic salt;

(D) optionally, but preferably, from about 0% to about 3%, by weight ofthe composition, of solubilizing aid; and

(E) aqueous carrier; and

wherein said composition is essentially free of any material that wouldsoil or stain fabric and wherein said composition contains less thanabout 5%, by weight of the composition of low molecular weightmonohydric alcohols.

I. COMPOSITION (A) PERFUME

The perfume selected for use in the fabric freshening composition of thepresent invention contains ingredients with odor characteristics whichare preferred in order to provide a fresh impression on the surface towhich the composition is directed, preferably those which provide afresh impression for fabrics.

Preferably, at least about 25%, more preferably at least about 50%, mostpreferably at least about 75%, by weight of the perfume is composed offragrance material selected from the group consisting of aromatic andaliphatic esters having molecular weights from about 130 to about 250;aliphatic and aromatic alcohols having molecular weights from about 90to about 240; aliphatic ketones having molecular weights from about 150to about 260; aromatic ketones having molecular weights from about 150to about 270; aromatic and aliphatic lactones having molecular weightsfrom about 130 to about 290; aliphatic aldehydes having molecularweights from about 140 to about 200; aromatic aldehydes having molecularweights from about 90 to about 230; aliphatic and aromatic ethers havingmolecular weights from about 150 to about 270; and condensation productsof aldehydes and amines having molecular weights from about 180 to about320; and essentially free from nitromusks and halogenated flagrancematerials.

More preferably, at least about 25%, more preferably at least about 50%,most preferably at least about 75%, by weight of the perfume is composedof fragrance material selected from the group consisting of:

    __________________________________________________________________________                                            Approx.                               Common Name    Chemical Type                                                                          Chemical Name   M.W.                                  __________________________________________________________________________    adoxal         aliphatic aldehyde                                                                     2,6,10-trimethyl-9-undecen-1-al                                                               210                                   allyl amyl glycolate                                                                         ester    allyl amyl glycolate                                                                          182                                   allyl cylohexane propionate                                                                  ester    allyl-3-cyclohexyl propionate                                                                 196                                   amyl acetate   ester    3-methyl-1-butanol acetate                                                                    130                                   amyl salicylate                                                                              ester    amyl salicylate 208                                   anisic aldehyde                                                                              aromatic aldehyde                                                                      4-methoxy benzaldehyde                                                                        136                                   aurantiol      schiff base                                                                            condensation product of methyl                                                                305                                                           anthranilate and                                                              hydroxycitronellal                                    bacdanol       aliphatic alcohol                                                                      2-ethyl-4-(2,2,3-trimethyl-3-                                                                 208                                                           cyclopenten-1-yl)-2-buten-1-ol                        benzaldehyde   aromatic aldehyde                                                                      benzaldehyde    106                                   benzophenone   aromatic ketone                                                                        benzophenone    182                                   benzyl acetate ester    benzyl acetate  150                                   benzyl salicylate                                                                            ester    benzyl salicylate                                                                             228                                   beta damascone aliphatic ketone                                                                       1-(2,6,6-trimethyl-1-cyclo-hexen-                                                             192                                                           1-yl)-2-buten-1-one                                   beta gamma hexanol                                                                           alcohol  3-hexen-1-ol    100                                   buccoxime      aliphatic ketone                                                                       1,5-dimethyl-oxime bicyclo[3,2,1]                                                             167                                                           octan-8-one                                           cedrol         alcohol  octahydro-3,6,8,8-tetramethyl-                                                                222                                                           1H-3A,7-methanoazulen-6-ol                            cetalox        ether    dodecahydro-3A,6,6,9A-                                                                        236                                                           tetramethylnaphtho[2,1B]-furan                        cis-3-hexenyl acetate                                                                        ester    cis-3-hexenyl acetate                                                                         142                                   cis-3-hexenyl salicylate                                                                     ester    beta, gamma-hexenyl salicylate                                                                220                                   citronellol    alcohol  3,7-dimethyl-6-octenol                                                                        156                                   citronellyl nitrile                                                                          nitrile  geranyl nitrite 151                                   clove stem oil natural                                                        coumarin       lactone  coumarin        146                                   cyclohexyl salicylate                                                                        ester    cyclohexyl salicylate                                                                         220                                   cymal          aromatic aldehyde                                                                      methyl-3-(para iso propyl                                                                     190                                                           phenyl)propionaldehyde                                decyl aldehyde aliphatic aldehyde                                                                     decyl aldehyde  156                                   delta damascone                                                                              aliphatic ketone                                                                       1-(2,6,6-trimethyl-3-cyclo-hexen-                                                             192                                                           1-yl)-2-buten-1-one                                   dihydromyrcenol                                                                              alcohol  3-methylene-7-methyl octan-7-ol                                                               156                                   dimethyl benzyl carbinyl                                                                     ester    dimethyl benzyl carbinyl acetate                                                              192                                   acetate                                                                       ethyl vanillin aromatic aldehyde                                                                      ethyl vanillin  166                                   ethyl-2-methyl butyrate                                                                      ester    ethyl-2-methyl butyrate                                                                       130                                   ethylene brassylate                                                                          macrocyclic                                                                            ethylene tridecan-1,13-dioate                                                                 270                                                  lactone                                                        eucalyptol     aliphatic epoxide                                                                      1,8-epoxy-para-menthane                                                                       154                                   eugenol        alcohol  4-allyl-2-methoxy phenol                                                                      164                                   exaltolidc     macrocyclic                                                                            cyclopentadecanolide                                                                          240                                                  lactone                                                        flor acetate   ester    dihydro-nor-cyclopentadienyl                                                                  190                                                           acetate                                               florhydral     aromatic aldehyde                                                                      3(3-isopropylphenyl) butanal                                                                  190                                   frutene        ester    dihydro-nor-cyclopentadienyl                                                                  206                                                           propionate                                            gataxolide     ether    1,3,4,6,7,8-hexahydro-                                                                        258                                                           4,6,6,7,8,8-                                                                  hexamethylcyclopenta-gamma-2-                                                 benzopyrane                                           gamma decalactone                                                                            lactone  4-N-hepty-4-hydroxybutanoic                                                                   170                                                           acid lactone                                          gamma dodecalactone                                                                          lactone  4-N-octyl-4-hydroxy-butanoic                                                                  198                                                           acid lactone                                          geraniol       alcohol  3,7-dimethyl-2,6-octadien-1-ol                                                                154                                   geranyl acetate                                                                              ester    3,7-dimethyl-2,6-octadien-1-yl                                                                196                                                           acetate                                               geranyl nitrile                                                                              ester    3,7-diemthyl-2,6-octadienenitrile                                                             149                                   helional       aromatic aldehyde                                                                      alpha-methyl-3,4,                                                                             192                                                           (methylenedioxy)                                                              hydrocinnamaldehyde                                   heliotropin    aromatic aldehyde                                                                      heliotropin     150                                   hexyl acetate  ester    hexyl acteate   144                                   hexyl cinnamic aldehyde                                                                      aromatic aldehyde                                                                      alpha-n-hexyl cinnamic aldehyde                                                               216                                   hexyl salicylate                                                                             ester    hexyl salicylate                                                                              222                                   hydroxyambran  aliphatic alcohol                                                                      2-cyclodecyl-propanol                                                                         226                                   hydroxycitronellal                                                                           aliphatic aldehyde                                                                     hydroxycitronellal                                                                            172                                   ionone alpha   aliphatic ketone                                                                       4-(2,6,6-trimethyl-1-                                                                         192                                                           cyclohexenyl-1-yl)-3-buten-2-one                      ionone beta    aliphatic ketone                                                                       4-(2,6,6-trimethyl-1-cyclohexen-                                                              192                                                           1-yl)-3-butene-2-one                                  ionone gamma methyl                                                                          aliphatic ketone                                                                       4-(2,6,6-trimethyl-2-cyclohexyl-                                                              206                                                           1-yl)-3-methyl-3-buten-2-one                          iso E super    aliphatic ketone                                                                       7-acetyl-1,2,3,4,5,6,7,8-                                                                     234                                                           octahydro-1,1,6,7,tetramethyl                                                 naphthalene                                           iso eugenol    ether    2-methoxy-4-(1-propenyl)phenol                                                                164                                   iso jasmone    aliphatic ketone                                                                       2-methyl-3-(2-pentenyl)-2-                                                                    166                                                           cyclopenten-1-one                                     koavone        aliphatic aldehyde                                                                     acetyl di-isoamylene                                                                          182                                   lauric aldehyde                                                                              aliphatic aldehyde                                                                     lauric aldehyde 184                                   lavandin       natural                                                        lavender       natural                                                        lemon CP       natural  major component                                                               d-limonene                                            d-limonene/orange terpenes                                                                   alkene   1-methyl-4-iso-propenyl-1-                                                                    136                                                           cyclohexene                                           linalool       alcohol  3-hydroxy-3,7-dimethyl-1,6-                                                                   154                                                           octadiene                                             linatyl acetate                                                                              ester    3-hydroxy-3,7-dimethyl-1,6-                                                                   196                                                           octadiene acetate                                     Irg 201        ester    2,4-dihydroxy-3,6-dimethyl                                                                    196                                                           benzoic acid methyl ester                             lyral          aliphatic aldehyde                                                                     4-(4-hydroxy-4-methyl-pentyl) 3-                                                              210                                                           cylcohexene-1-carboxaldehyde                          majantol       aliphatic alcohol                                                                      2,2-dimethyl-3-(3-methylphenyl)-                                                              178                                                           propanol                                              mayol          alcohol  4-(1-methylethyl) cyclohexane                                                                 156                                                           methanol                                              methyl anthranilate                                                                          aromatic amine                                                                         methyl-2-aminobenzoale                                                                        151                                   methyl beta naphthyl ketone                                                                  aromatic ketone                                                                        methyl beta naphthyl ketone                                                                   170                                   methyl cedrylone                                                                             aliphatic ketone                                                                       methyl cedrenyl ketone                                                                        246                                   methyl chavicol                                                                              ester    1-methyloxy-4,2-propen-                                                                       148                                                           1-yl benzene                                          methyl dihydro jasmoriate                                                                    aliphatic ketone                                                                       methyl dihydrojasmonate                                                                       226                                   methyl nonyl acetaldehyde                                                                    aliphatic aldehyde                                                                     methyl nonyl acetaldehyde                                                                     184                                   musk indanone  aromatic ketone                                                                        4-acetyl-6-tert butyl-1,1-dimethyl                                                            244                                                           indane                                                nerol          alcohol  2-cis-3,7-dimethyl-2,6-octadien-                                                              154                                                           1-ol                                                  nonalactone    lactone  4-hydroxynonanoic acid, lactone                                                               156                                   norlimbanol    aliphatic alcohol                                                                      1-(2,2,6-trimethyl-cyclohexyl)-3-                                                             226                                                           hexanol                                               orange CP      natural  major component                                                               d-limonene                                            P. T. bucinal  aromatic aldehyde                                                                      2-methyl-3(para tert butylphenyl)                                                             204                                                           propionaldehyde                                       para hydroxy phenyl butanone                                                                 aromatic ketone                                                                        para hydroxy phenyl butanone                                                                  164                                   patchouti      natural                                                        phenyl acetaldehyde                                                                          aromatic aldehyde                                                                      1-oxo-2-phenylethane                                                                          120                                   phenyl acetaldehyde dimethyl                                                                 aromatic aldehyde                                                                      phenyl acetaldehyde dimethyl                                                                  166                                   acetal                  acetal                                                phenyl ethyl acetate                                                                         ester    phenyl ethyl acetate                                                                          164                                   phenyl ethyl alcohol                                                                         alcohol  phenyl ethyl alcohol                                                                          122                                   phenyl ethyl phenyl acetate                                                                  ester    2-phenylethyl phenyl acetate                                                                  240                                   phenyl hexanol/phenoxanol                                                                    alcohol  3-methyl-5-phenylpentanol                                                                     178                                   polysantol     aliphatic alcohol                                                                      3,3-dimethyl-5-(2,2,3-trimethyl-                                                              221                                                           3--cyclopenten-                                                               1-yl)4-penten-2-ol                                    prenyl acetate ester    2-methylbuten-2-ol-4-acetate                                                                  128                                   rosaphen       aromatic alcohol                                                                       2-methyl-5-phepyl pentanol                                                                    178                                   sandalwood     natural                                                        alpha-terpinene                                                                              aliphatic alkane                                                                       1-methyl-4-iso- 136                                                           propylcyclohexadiene-1,3                              terpineol (alpha terpineol and                                                               alcohol  para-menth-1-en-8-ol, para-                                                                   154                                   beta terpineol)         menth-1-en-1-ol                                       terpinyl acetate                                                                             ester    para-menth-1-en-8-yl acetate                                                                  196                                   tetra hydro linalool                                                                         aliphtic alcohol                                                                       3,7-dimethyl-3-octanol                                                                        158                                   tetrahydromyrcenol                                                                           aliphatic alcohol                                                                      2,6-dimethyl-2-octanol                                                                        158                                   tonalid/musk plus                                                                            aromatic ketone                                                                        7-acetyl-1,1,3,4,4,6-hexamethyl                                                               258                                                           tetralin                                              undecalactone  lactone  4-N-heptyl-4-hydroxybutanoic                                                                  184                                                           acid lactone                                          undecavertol   alcohol  4-methyl-3-decen-5-ol                                                                         170                                   undecyl aldehyde                                                                             aliphatic aldehyde                                                                     undecanal       170                                   undecylenic aldehyde                                                                         aliphatic aldehyde                                                                     undecylenic aldehyde                                                                          168                                   vanillin       aromatic aldehyde                                                                      4-hydroxy-3-    152                                                           methoxybenezaldehyde                                  verdox         ester    2-tert-butyl cyclohexyl acetate                                                               198                                   vertenex       ester    4-tert-butyl cyclohexyl acetate                                                               198                                   __________________________________________________________________________

and mixtures thereof.

When high initial perfume odor impact on fabrics is desired, it is alsopreferable to select a perfume containing perfume ingredients which arenot too hydrophobic. The less hydrophobic perfume ingredients are moresoluble in water, and are more available in the freshening composition.The degree of hydrophobicity of a perfume ingredient can be correlatedwith its octanol/water partitioning coefficient P. The octanol/waterpartitioning coefficient of a perfume ingredient is the ratio betweenits equilibrium concentration in octanol and in water. A perfumeingredient with a greater partitioning coefficient P is morehydrophobic. Conversely, a perfume ingredient with a smallerpartitioning coefficient P is more hydrophilic. The preferred perfumeingredients of this invention have an octanol/water partitioningcoefficient P of about 1,000 or smaller. Since the partitioningcoefficients of the perfume ingredients normally have high values, theyare more conveniently given in the form of their logarithm to the base10, logP. Thus the perfume ingredients of this invention have IogP ofabout 3 or smaller.

The logP of many perfume ingredients has been reported; for example, thePomona 92 database, available from Daylight Chemical InformationSystems, Inc. (Daylog CIS), Irvine, Calif., contains many, along withcitations to the original literature. However, the IogP values are mostconveniently calculated by the "CLOG P" program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona 92 database. The "calculated logP" (Clog P)is determined by the fragment approach of Hansch and Leo (cf., A. Leo,in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens,J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each perfume ingredient, and takes into accountthe numbers and types of atoms, the atom connectivity, and chemicalbonding. The Clog P values, which are the most reliable and widely usedestimates for this physicochemical property, are used instead of theexperimental logP values in the selection of perfume ingredients whichare useful in the present invention.

Non-limiting examples of perfume ingredients which have Clog P values ofabout 3 or smaller are benzaldehyde, benzyl acetate, cis-3-hexenylacetate, coumarin, dihydromyrcenol, dimethyl benzyl carbinyl acetate,ethyl vanillin, eucalyptol, eugenol, iso eugenol, flor acetate,geraniol, hydroxycitronellal, koavone, linalool, methyl anthranilate,methyl beta naphthyl ketone, methyl dihydro jasmonate, nerol,nonalactone, phenyl ethyl acetate, phenyl ethyl alcohol, alphaterpineol, beta terpineol, vanillin, and mixtures thereof.

When hydrophilic perfume is desired, at least about 25% by weight of theperfume, more preferably about 50%, most preferably about 75%, iscomposed of perfume ingredients having a Clog P of about 3 or smaller.

Preferably the freshening composition contains an effective amount ofperfume to provide the freshening fragrance to fabrics when firstsprayed, some lingering fragrance in-wear, and some extra flagrance tobe released upon fabric rewetting. Effective level of perfume is fromabout 0.01% to about 1%, more preferably from about 0.01% to about 0.5%,most preferably from about 0.015% to about 0.3%, by weight of thecomposition. When cyclodextrin is added to the composition of thepresent invention, the perfume to cyclodextrin weight ratio is typicallyfrom about 3:100 to about 100:100, preferably from about 4:100 to about50:100, more preferably from about 5:100 to about 40:100, even morepreferably from about 5:100 to about 25:100, most preferably from about1:8 to about 1:4.

(B) CYCLODEXTRIN

Optionally, but preferably, solubilized, water-soluble, uncomplexedcyclodextrin can be added to the composition of the present invention.As used herein, the term "cyclodextrin" includes any of the knowncyclodextrins such as unsubstituted cyclodextrins containing from six totwelve glucose units, especially, alpha-cydodextrin, beta-cyclodextrin,gamma-cyclodextrin and/or their derivatives and/or mixtures thereof. Thealpha-cyclodextrin consists of six glucose units, the beta-cyclodextrinconsists of seven glucose units, and the gamma-cyclodextrin consists ofeight glucose units arranged in a donut-shaped ring. The specificcoupling and conformation of the glucose units give the cydodextrins arigid, conical molecular structure with a hollow interior of a specificvolume. The "lining" of the internal cavity is formed by hydrogen atomsand glycosidic bridging oxygen atoms, therefore this surface is fairlyhydrophobic. The unique shape and physical-chemical property of thecavity enable the cydodextrin molecules to absorb (form inclusioncomplexes with) organic molecules or parts of organic molecules whichcan fit into the cavity. Many perfume molecules can fit into the cavity.

Non-derivatised (normal) beta-cyclodextrin can be used although it isnot preferred due to its low solubility. When non-derivatisedbeta-cyclodextrin is used, the aqueous solution becomes cloudy and isnot clear, as preferred by the present invention. Not to be limited bytheory, it is believed that some beta-cyclodextrin and/orbeta-cydodextrin/perfume complexes solidify and/or precipitate outproducing an undesirable cloudy aqueous solution.

Preferably, the odor absorbing solution of the present invention isclear. The term "dear" as defined herein means transparent ortranslucent, preferably transparent as in "water clear," when observedthrough a layer having a thickness of less than about 10 cm.

Preferably, the cyclodextrins used in the present invention are highlywater-soluble such as, alpha-cyclodextrin and derivatives thereof,gamma-cyclodextrin and derivatives thereof, derivatisedbeta-cyclodextrins, and/or mixtures thereof. The derivatives ofcyclodextrin consist mainly of molecules wherein some of the OH groupsare converted to OR groups. Cyclodextrin derivatives include, e.g.,those with short chain alkyl groups such as methylated cyclodextrins,and ethylated cyclodextrins, wherein R is a methyl or an ethyl group;those with hydroxyalkyl substituted groups, such as hydroxypropylcyclodextrins and/or hydroxyethyl cyclodextrins, wherein R is a --CH₂--CH(OH)--CH₃ or a --CH₂ CH₂ --OH group; branched cyclodextrins such asmaltose bonded cyclodextrins; cationic cyclodextrins such as thosecontaining 2-hydroxy-3(dimethylarnino)propyl ether, wherein R is CH₂--CH(OH)--CH₂ --N(CH₃)₂ which is cationic at low pH; quaternaryammonium, e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloridegroups, wherein R is CH₂ --CH(OH)--CH₂ --N+(CH₃)₃ Cl--; anioniccyclodextrins such as carboxymethyl cyclodextrins, cyclodextrinsulfates, and cyclodextrin succinylates; amphoteric cyclodextrins suchas carboxymethyl/quaternary ammonium cyclodextrins; cyclodextrinswherein at least one glucopyranose unit has a 3-6-anhydro-cyclomaltostructure, e.g., the mono-3-6-anhydrocyclodextrins, as disclosed in"Optimal Performances with Minimal Chemical Modification ofCyclodextrins", F. Diedainl-Pilard and B. Perly, The 7th InternationalCyclodextrin Symposium Abstracts, April 1994, p. 49, herein incorporatedby reference; and mixtures thereof. Other cyclodextrin derivatives aredisclosed in U.S. Pat. Nos: 3,426,011, Parmerter et al., issued Feb. 4,1969; 3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the namesof Parmerter et al., and all issued Jul. 1, 1969; 3,459,731, Gramera etal., issued Aug. 5, 1969; 3,553,191, Parmerter et at., issued Jan. 5,1971; 3,565,887, Parmerter et al., issued Feb. 23, 1971; 4,535,152,Szejtli et al., issued Aug. 13, 1985; 4,616,008, Hirai et al., issuedOct. 7, 1986; 4,678,598, Ogino et al., issued Jul. 7, 1987; 4,638,058,Brandt et at., issued Jan. 20, 1987; and 4,746,734, Tsuchiyama et al.,issued May 24, 1988; all of said patents being incorporated herein byreference.

Highly water-soluble cyclodextrins are those having water solubility ofat least about 10 g in 100 ml of water at room temperature, preferablyat least about 20 g in 100 ml of water, more preferably at least about25 g in 100 ml of water at room temperature. Examples of preferredwater-soluble cyclodextrin derivatives suitable for use herein arehydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin,methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, andhydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivativespreferably have a degree of substitution of from about 1 to about 14,more preferably from about 1.5 to about 7, wherein the total number ofOR groups per cyclodextrin is defined as the degree of substitution.Methylated cyclodextrin derivatives typically have a degree ofsubstitution of from about 1 to about 18, preferably from about 3 toabout 16. A known methylated beta-cyclodextrin isheptakis-2,6-di-O-methyl-β-cyclodextrin, commonly known as DIMEB, inwhich each glucose unit has about 2 methyl groups with a degree ofsubstitution of about 14. A preferred, more commercially availablemethylated beta-cyclodextrin is a randomly methylated beta-cyclodextrinhaving a degree of substitution of about 12.6. The preferredcyclodextrins are available, e.g., from American Maize-Products Companyand Wacker Chemicals (USA), Inc.

It is also preferable to use a mixture of cyclodextrins. Such mixturescan complex with a wider range of perfume molecules having a wider rangeof molecular sizes. Preferably at least a portion of the cyclodextrinsis alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrinand its derivatives thereof, and/or derivatised beta-cyclodextrin, andmixtures thereof.

Cyclodextrin molecules are known for their ability to form complexeswith perfume ingredients and have typically been taught as a perfumecarrier. The prior art teaches the use of drier-added fabric softenersheets containing high levels of cyclodextrin/perfume complexes whereinthe fabrics treated with this solid cyclodextrin complex release perfumewhen the fabrics are rewetted. The art also teaches thatcyclodextrin/perfume complexes used in aqueous rinse-added fabricsoftener compositions must be protected, e.g., with a hydrophobic waxcoating so the cyclodextrin/perfume complexes will not decompose due tothe presence of water. See U.S. Pat. Nos. 5,102,564 Gardlik et at.,issued Apr. 7, 1992; 5,234,610, Gardlik et at., issued Aug. 10, 1993;5,234,611 Trinh, et al., issued Aug. 10, 1993, all of said patentsincorporated herein by reference. It is therefore highly surprising andunexpected to find that fabrics treated with the aqueous compositions ofthe present invention, which contain low levels of unprotectedcyclodextrin, also exhibit perfume release upon rewetting. Thisphenomenon provides a benefit in that fabrics treated with thecomposition of the present invention will thus remain fresh longer, viaa perfume release, when said fabrics are rewetted, such as when thewearer perspires.

For reducing malodor impression on fabrics, the composition ispreferably used as a spray. It is preferable that the composition of thepresent invention contain low levels of cyclodextrin so that a visiblestain does not appear on the fabric at normal usage levels. Preferably,the solution is not discernible when dry. Typical levels of cyclodextrinare from about 0.1% to about 5%, preferably from about 0.2% to about 4%,more preferably from about 0.3% to about 3%, most preferably from about0.4% to about 2%, by weight of the composition. Compositions with higherconcentrations can leave unacceptable visible stains on fabrics as thesolution evaporates off of the fabric. This is especially a problem onthin, colored, synthetic fabrics. In order to avoid or minimize theoccurrence of fabric staining, it is preferable that the fabric betreated at a level of less than about 5 mg of cyclodextrin per mg offabric, more preferably less than about 2 mg of cyclodextrin per mg offabric.

Concentrated compositions can also be used in order to provide a lessexpensive product. When a concentration is used, i.e., when the level ofcyclodextrin used is from about 3% to about 5% it is preferable todilute the composition before treating fabrics in order to avoidstaining. Preferably the cyclodextrin is diluted with about 50% to about2000%, more preferably with about 60% to about 1000%, most preferablywith about 75% to about 500%, by weight of the composition, of water.

(C) METALLIC SALT

Optionally, but preferably, metallic salt, preferably water-soluble zincsalts, can be added to the composition of the present invention. Awater-soluble metallic salt can be used as an odor control agent. Awater-soluble metallic salt can be present in the freshening compositionof the present invention to absorb amine and sulfur-containingcompounds. Furthermore, they usually do not contribute an odor of theirown. Preferably the water-soluble metallic salts are selected from thegroup consisting of copper salts, zinc salts, and mixtures thereof.

The preferred zinc salts have been used most often for their ability toameliorate malodor, e.g., in mouth wash products, as disclosed in U.S.Pat. Nos. 4,325,939, issued Apr. 20, 1982 and 4,469,674, issued Sep. 4,1983, to N. B. Shah, et al., incorporated herein by reference. U.S. Pat.No. 3,172,817, issued to Leupold, et al., discloses deodorizingcompositions containing slightly water-soluble salts of an acyl-acetonewith a polyvalent metal, including copper and zinc salts. Said patentsare incorporated herein by reference.

Examples of preferred water-soluble zinc salts are zinc chloride, zincgluconate, zinc lactate, zinc maleate, zinc salicylate, zinc sulfate,etc. Highly-ionized and soluble zinc salts such as zinc chloride,provide the best source of zinc ions. Examples of preferred copper saltsare copper chloride and copper gluconate. Preferred metallic salts arezinc chloride and copper chloride.

Metallic salts are added to the composition of the present inventiontypically at a level of from about 0.1% to about 10%, preferably fromabout 0.2% to about 7%, more preferably from about 0.3% to about 5%, byweight of the composition. When zinc salts are used as the metallicsalt, and a clear solution is desired, it is preferable that the pH ofthe solution is adjusted to less than about 7, more preferably less thanabout 6, most preferably, less than about 5, in order to keep thesolution clear.

(D) SOLUBILIZING AID

The freshening composition of the present invention can optionally, butpreferably, contain a solubilizing aid to solubilize any excesshydrophobic organic materials, especially the perfume, and also optionalingredients which can be added to the composition, e.g., insectrepelling agent, antioxidant, etc., that are not readily soluble in thecomposition, to form a clear solution. A suitable solubilizing aid issurfactant, preferably no-foaming or low-foaming surfactant. Suitablesurfactants are nonionic surfactants, cationic surfactants, amphotericsurfactants, zwitterionic surfactants, and mixtures thereof, preferablynonionic surfactants and cationic surfactants, and mixtures thereof.Anionic surfactants are not preferred, because they can formwater-insoluble salts with the metal ions of the preferred metallicsalts of this composition. Suitable surfactants can be emulsifiersand/or detersive surfactants. Mixtures of emulsifiers and detersivesurfactants are also preferred. When a surfactant containing one, ormore, alkyl group is used, it is preferred that it contain relativelyshort alkyl chains of from about 5 to about 14 carbon atoms. Preferrednonionic surfactants are polyethylene glycol-polypropylene glycol blockcopolymers, such as Pluronic® and Pluronic R® surfactants from BASF;Tetronic® and Tetronic R® surfactants from BASF, ethoxylated branchedaliphatic diols, such as Surfynol® surfactants from Air Products;ethoxylated alkyl phenols, such as Igepal® surfactants fromRhone-Poulenc; ethoxylated aliphatic alcohols and carboxylic acids;polyethylene glycol diesters of fatty acids; fatty acid esters ofethoxylated sorbitans; and mixtures thereof. Preferred cationicsurfactants are di(C₈ -Cl₂ alkyl)di(C₁ -Cl₂ alkyl)ammonium halides,alkylbenzyldimethylammonium halides, amine oxides, and mixtures thereof.Preferred amphoteric surfactants are the betaines. It is preferred thatthe surfactant have good wetting properties. Also preferred aresurfactants that have the hydrophilic groups between hydrophobic chains,such as, Pluronic R surfactants, Surfynol surfactants, polyethyleneglycol diesters of fatty acids, fatty acid esters of ethoxylatedsorbitans, di(C₈ -Cl₂ alkyl)di(C1-C2 alkyl)ammonium halides, andmixtures thereof; surfactants that have hydrophilic groups situated atthe extremities of the hydrophobic chain, such as Pluronic surfactants;and mixtures thereof. Mixtures of these surfactants and other types ofsurfactants are also preferred to form no-foaming or low-foamingsolubilizing agents. Polyalkylene glycol can be used as defoaming agentin combination with the solubilizing agents.

When the solubilizing agent is present, it is typically present at alevel of from about 0.05% to about 3%, by weight of the composition,more preferably from about 0.05% to about 1%, by weight of thecomposition, most preferably from about 0.1% to about 0.3%, by weight ofthe composition.

(E) AQUEOUS CARRIER

Aqueous solutions are preferred in the present invention for thereduction of malodor impression. The preferred aqueous carrier of thepresent invention is water. The water which is used can be distilled,deionized, or tap water. Water containing a small amount of lowmolecular weight monohydric alcohols, e.g., ethanol, methanol, andisopropanol, or polyols, such as ethylene glycol and propylene glycol,can also be useful. However, the volatile low molecular weightmonohydric alcohols such as ethanol and/or isopropanol should be limitedsince these volatile organic compounds will contribute both toflammability problems and environmental pollution problems. If smallamounts of low molecular weight monohydric alcohols are present in thecomposition of the present invention due to the addition of thesealcohols to such things as perfumes and as stabilizers for somepreservatives, it is preferably that the level of monohydric alcohol beless than about 5%, preferably less than about 3%, more preferably lessthan about 1%, by weight of the composition.

It has recently been discovered that water has an unexpected odorcontrolling effect of its own. It has been discovered that the intensityof the odor generated by some polar, low molecular weight organicamines, acids, and mercaptans is reduced when the odor-contaminatedfabrics are treated with an aqueous solution. Not to be bound by theory,it is believed that water solubilizes and depresses the vapor pressureof these polar, low molecular weight organic molecules, thus reducingtheir odor intensity.

(F) OTHER OPTIONAL INGREDIENTS

Adjuvants can be optionally added to the freshening composition hereinfor their known purposes. Such adjuvants include, but are not limitedto, preservatives, defoaming agents, antifoaming agents, bacteriocides,fungicides, antistatic agents, insect and moth repelling agents,colorants, especially bluing agents, antioxidants, and mixtures thereof.

(1) Preservative

Optionally, solubilized, water-soluble preservatives can be added to thepresent invention. Preservatives are especially preferred whencyclodextrin is added to the composition of the present inventionbecause cyclodextrin molecules are made up of varying numbers of glucoseunits which can make them a prime breeding ground for certainmicroorganisms, especially when in aqueous compositions. This drawbackcan lead to the problem of storage stability of cyclodextrin solutionsfor any significant length of time. Contamination by certainmicroorganisms with subsequent microbial growth resulting in anunsightly and/or malodorous solution. Because microbial growth incyclodextrin solutions is highly objectionable when it occurs, it ispreferable to include a solubilized water-soluble, antimicrobialpreservative, which is effective for inhibiting and/or regulatingmicrobial growth in order to increase storage stability of thepreferably clear, aqueous odor-absorbing solution containingwater-soluble cyclodextrin.

Typical microorganisms that can be found in cyclodextrin supplies andwhose growth can be found in the presence of cyclodextrin in aqueouscyclodextrin solutions include bacteria, e.g., Bacillus thuringiensis(cereus group) and Bacillus sphaeficus; and fungi, e.g., Aspergillusustus.Bacillus sphaericus is one of the most numerous members ofBacillus species in soils. Aspergillus ustus is common in grains andflours which are raw materials to produce cyclodextrins. Microorganismssuch as Escherichia coli and Pseudomonas aeruginosa are found in somewater sources, and can be introduced during the preparation ofcyclodextrin aqueous solutions.

It is preferable to use a broad spectrum preservative, e.g., one that iseffective on both bacteria (both gram positive and gram negative) andfungi. A limited spectrum preservative, e.g., one that is only effectiveon a single group of microorganisms, e.g., fungi, can be used incombination with a broad spectrum preservative or other limited spectrumpreservatives with complimentary and/or supplementary activity. Amixture of broad spectrum preservatives can also be used.

Antimicrobial preservatives useful in the present invention can bebiocidal compounds, i.e., substances that kill microorganisms, orbiostatic compounds, i.e., substances that inhibit and/or regulate thegrowth of microorganisms.

Preferred antimicrobial preservatives are those that are water-solubleand are effective at low levels because the organic preservatives canform inclusion complexes with the cyclodextrin molecules and competewith the perfume molecules for the cyclodextrin cavities, thus renderingthe complexed preservatives much less effective. Water-solublepreservatives useful in the present invention are those that have asolubility in water of at least about 0.3 g per 100 ml of water, i.e.,about 0.3% at room temperature, preferably greater than about 0.5% atroom temperature. These types of preservatives have a lower affinity tothe cyclodextrin cavity, at least in the aqueous phase, and aretherefore more available to provide antimicrobial activity.Preservatives with a water-solubility of less than about 0.3% and amolecular structure that readily fits into the cyclodextrin cavity, havea greater tendency to form inclusion complexes with the cyclodextrinmolecules, thus rendering the preservative less effective to controlmicrobes in the cyclodextrin solution. Therefore, many well knownpreservatives such as short chain alkyl esters of p-hydroxybenzoic acid,commonly known as parabens; N-(4-chlorophenyl)-N '-(3,4-dichlorophenyl)urea, also known as 3,4,4'-trichloroearbanilide or triclocarban;2,4,4'-trichloro-2'-hydroxy diphenyl ether, commonly known as triclosanare not preferred in the present invention since they are relativelyineffective when used in conjunction with cyclodextrin.

The water-soluble antimicrobial preservative is included in the presentinvention it is included at an effective amount. The term "effectiveamount" as herein defined means a level sufficient to prevent spoilageor prevent growth of inadvertently added microorganisms for a specificperiod of time, but not sufficient enough to contribute to the odorabsorbing performance of the composition. In other words, thepreservative is not being used to kill microorganisms on the surfaceonto which the composition is deposited in order to eliminate odorsproduced by microorganisms. Instead, it is preferably being used toprevent spoilage of the cyclodextrin solution in order to increase theshelf-life of the composition. Preferred levels of preservative are fromabout 0.0001% to about 0.5%, more preferably from about 0.0002% to about0.2%, most preferably from about 0.0003% to about 0.1%, by weight of thecomposition.

The preservative can be any organic preservative material which will notcause damage to fabric appearance, e.g., discoloration, coloration,bleaching. Preferred water-soluble preservatives include organic sulfurcompounds, halogenated compounds, cyclic organic nitrogen compounds, lowmolecular weight aldehydes, quaternary compounds, dehydroacetic acid,phenyl and phenoxy compounds, and mixtures thereof.

Non-limiting examples of the preferred water-soluble preservatives foruse in the present invention include a mixture of about 77%5-chloro-2-methyl-4-isothiazolin-3-one and about 23%2-methyl-4-isothiazolin-3-one, a broad spectrum preservative availableas a 1.5% aqueous solution under the trade name Kathon® CG by Rohm andHaas Co.; 5-bromo-5-nitro-1,3-dioxane, available under the trade nameBronidox L® from Henkel; 2-bromo-2-nitropropane-1,3-diol, availableunder the trade name Bronopol® from Inolex; 1,1 '-hexamethylenebis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, andits salt 95:5 mixture of1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and3-butyl-2-iodopropynyl carbamate, available under the trade name GlydantPlus® from Lonza;N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'-bis(hydroxy-methyl) urea, commonly known as diazolidinyl urea,available under the trade name Germall II® from Sutton Laboratories,Inc.;N,N"-methylenebis{N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea},commonly known as imidazolidinyl urea, available, e.g., under the tradename Abiol® from 3V-Sigma, Unicide U-13® from Induehem, Germall 115®from Sutton Laboratories, Inc.; polymethoxy bicyclic oxazolidine,available under the trade name Nuosept® C. from Hals America;formaldehyde; glutaraldehyde; polyaminopropyl biguanide; available underthe trade name Cosmocil CQ® from ICI Americas, Inc., or under the tradename Mikrokill® from Brooks, Inc; dehydroacetic acid; and mixturesthereof.

Bacteriostatic effects can sometimes be obtained for aqueouscompositions by adjusting the composition pH to an acid pH, e.g., lessthan about pH 4, preferably less than about pH 3. Low pH for microbialcontrol is not a preferred approach in the present invention because thelow pH can cause chemical degradation of the cyclodextrins. Therefore,aqueous compositions of the present invention should have a pH greaterthan about 3.0, preferably greater than about 4.0, more preferablygreater than about 4.5.

As stated above, it is preferable to use the preservative at aneffective amount, as defined hereinabove. Optionally however, thepreservative can be used at a level which provides an antimicrobialeffect on the treated fabrics.

(2) Antistatic Agents

The composition of the present invention can optionally contain aneffective mount of antistatic agent to provide the treated clothes within-wear static. Preferred antistatic agents are those that are watersoluble in at least effective amount, such that the composition remainsa clear solution. Examples of these antistatic agents are monoalkylcationic quaternary ammonium compounds, e.g., mono(C₁₀ -C₁₄alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammoniumchloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride,available under the trade name Dehyquart E® from Henkel, and ethylbis(polyethoxy ethanol) alkylammonium ethylsulfate, available under thetrade name Variquat 66® from Witco Corp., polyethylene glycols,polymeric quaternary ammonium salts, such as polymers conforming to thegeneral formula:

--[N(CH₃)₂, (CH₂)₃ --NH--CO--NH-(CH₂)₃ --N(CH₃)₂ +--CH₂ CH₂ OCH₂ CH₂]--_(x) ²⁺ 2x[Cl⁻ ]

available under the trade name Mirapol A-15® from Rhone-Poulenc, and

--[N(CH₃)₂ --(CH₂)₃ --NH--CO--(CH₂)₄ --CO----OH--(CH₂)₃ --N(CH₃)₂ -(CH₂CH₂ OCH₂ CH₂ ]--_(x) +x[CL⁻ ], available under the trade name MirapolAD-1® from Rhone-Poulenc, quaternized polyethyleneimines,vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloridecopolymer, available under the trade name Gafquat HS-100® from GAF;triethonium hydrolyzed collagen ethosulfate, available under the tradename Quat-Pro E® from Maybrook; and mixtures thereof.

It is preferred that a no foaming, or low foaming, agent is used, toavoid foam formation during fabric treatment. It is also preferred thatpolyethoxylated agents such as polyethylene glycol or Variquat 66® arenot used when alpha-cyclodextrin is used. The polyethoxylate groups havea strong affinity to, and readily complex with, alpha-cyclodextrin whichin turn deplete the uncomplexed cyclodextrin available for the perfume.

When an antistatic agent is used it is typically present at a level offrom about 0.05% to about 10%, preferably from about 0.1% to about 5%,more preferably from about 0.3% to about 3%, by weight of thecomposition.

(3) Insect and/or Moth Repelling Agent

The composition of the present invention can optionally contain aneffective amount of insect and/or moth repelling agents. Typical insectand moth repelling agents are pheromones, such as anti-aggregationpheromones, and other natural and/or synthetic ingredients. Preferredinsect and moth repellent agents useful in the composition of thepresent invention are perfume ingredients, such as citronellol,citranellal, citral, linalool, cedar extract, geranium oil, sandalwoodoil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc. Other examples ofinsect and/or moth repellents useful in the composition of the presentinvention are disclosed in U.S. Pat. Nos. 4,449,987, 4,693,890,4,696,676, 4,933,371, 5,030,660, 5,196,200, and in "Semio Activity ofFlavor and Fragrance Molecules on Various Insect Species", B. D.Mookherjee et al., published in Bioactive Volatile Compounds fromPlants, ASC Symposium Series 525, R. Teranishi, R. G. Buttery, and H.Sugisawa, 1993, pp. 35-48, all of said patents and publicationsincorporated herein by reference. When an insect and/or moth repellentis used it is typically present at a level of from about 0.005% to about3%,, by weight of the composition.

(4) Colorant

Colorants and dyes, especially bluing agents, can be optionally added tothe odor absorbing compositions for visual appeal and performanceimpression. When colorants are used, they are used at extremely lowlevels to avoid fabric staining. Preferred colorants for use in thepresent compositions are highly water-soluble dyes, e.g., Liquitint®dyes available from Milliken Chemical Co. Non-limiting examples ofsuitable dyes are, Liquitint Blue HP®, Liquitint Blue 65®, LiquitintPatent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow8949-43®, Liquitint Green HMC®, Liquitint Yellow II®, and mixturesthereof, preferably Liquitint Blue HP®, Liquitint Blue 65®, LiquitintPatent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow8949-43®, and mixtures thereof.

II. ARTICLE OF MANUFACTURE

The composition of the present invention can also be used in an articleof manufacture comprising said composition plus a spray dispenser.

SPRAY DISPENSER

The article of manufacture herein comprises a spray dispenser. Thecomposition for reducing malodor impression is placed into a spraydispenser in order to be distributed onto the fabric. Said spraydispenser is any of the manually activated means for producing a sprayof liquid droplets as is known in the art, e.g. trigger-type, pump-type,non-aerosol self-pressurized, and aerosol-type spray means. The spraydispenser herein does not include those that will substantially foam theclear, aqueous composition. It is preferred that at least about 80%,more preferably, at least about 90% of the droplets have a particle sizeof larger than about 30 μm

The spray dispenser can be an aerosol dispenser. Said aerosol dispensercomprises a container which can be constructed of any of theconventional materials employed in fabricating aerosol containers. Thedispenser must be capable of withstanding internal pressure in the rangeof from about 20 to about 110 p.s.i.g., more preferably from about 20 toabout 70 p.s.i.g. The one important requirement concerning the dispenseris that it be provided with a valve member which will permit the clear,aqueous odor absorbing composition contained in the dispenser to bedispensed in the form of a spray of very fine, or finely divided,particles or droplets. The aerosol dispenser utilizes a pressurizedsealed container from which the clear, aqueous odor-absorbingcomposition is dispensed through a special actuator/valve assembly underpressure. The aerosol dispenser is pressurized by incorporating thereina gaseous component generally known as a propellant. Common aerosolpropellants, e.g., gaseous hydrocarbons such as isobutane, and mixedhalogenated hydrocarbons, are not preferred. Halogenated hydrocarbonpropellants such as chlorofluoro hydrocarbons have been alleged tocontribute to environmental problems. Hydrocarbon propellants can formcomplexes with the cyclodextrin molecules thereby reducing theavailability of uncomplexed cyclodextrin molecules for odor absorption.Preferred propellants are compressed air, nitrogen, inert gases, carbondioxide, etc. A more complete description of commercially availableaerosol-spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbins,issued Apr. 8, 1969; and 3,600,325, Kaufman et al., issued Aug. 17,1971; both of said references are incorporated herein by reference.

Preferably the spray dispenser can be a self-pressurized non-aerosolcontainer having a convoluted liner and an elastomeric sleeve. Saidself-pressurized dispenser comprises a liner/sleeve assembly containinga thin, flexible radially expandable convoluted plastic liner of fromabout 0.010 to about 0.020 inch thick, inside an essentially cylindricalelastomeric sleeve. The liner/sleeve is capable of holding a substantialquantity of odor-absorbing fluid product and of causing said product tobe dispensed. A more complete description of self-pressurized spraydispensers can be found in U.S. Pat. Nos. 5,111,971, Winer, issued May12, 1992, and 5,232,126, Winer, issued Aug. 3, 1993; both of saidreferences are herein incorporated by reference. Another type of aerosolspray dispenser is one wherein a barrier separates the odor absorbingcomposition from the propellant (preferably compressed air or nitrogen),as disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981, andincorporated herein by reference. Such a dispenser is available from EPSpray Systems, East Hanover, N.J.

More preferably, the spray dispenser is a non-aerosol, manuallyactivated, pump-spray dispenser. Said pump-spray dispenser comprises acontainer and a pump mechanism which securely screws or snaps onto thecontainer. The container comprises a vessel for containing the aqueousodor-absorbing composition to be dispensed.

The pump mechanism comprises a pump chamber of substantially fixedvolume, having an opening at the inner end thereof. Within the pumpchamber is located a pump stem having a piston on the end thereofdisposed for reciprocal motion in the pump chamber. The pump stem has apassageway there through with a dispensing outlet at the outer end ofthe passageway and an axial inlet port located inwardly thereof.

The container and the pump mechanism can be constructed of anyconventional material employed in fabricating pump-spray dispensers,including, but not limited to: polyethylene; polypropylene;polyethyleneterephthalate; blends of polyethylene, vinyl acetate, andrubber elastomer. A preferred container is made of clear, e.g.,polyethylene terephthalate. Other materials can include stainless steel.A more complete disclosure of commercially available dispensing devicesappears in: U.S. Pat. Nos.: 4,895,279, Schultz, issued Jan. 23, 1990;4,735,347, Schultz et al., issued Apr. 5, 1988; and 4,274,560, Carter,issued Jun. 23, 1981; all of said references are herein incorporated byreference.

Most preferably, the spray dispenser is a manually activatedtrigger-spray dispenser. Said trigger-spray dispenser comprises acontainer and a trigger both of which can be constructed of any of theconventional material employed in fabricating trigger-spray dispensers,including, but not limited to: polyethylene; polypropylene; polyacetal;polycarbonate; polyethyleneterephthalate; polyvinyl chloride;polystyrene; blends of polyethylene, vinyl acetate, and rubberelastomer. Other materials can include stainless steel and glass. Apreferred container is made of clear, e.g. polyethylene terephthalate.The trigger-spray dispenser does not incorporate a propellant gas intothe odor-absorbing composition, and preferably it does not include thosethat will foam the odor-absorbing composition. The trigger-spraydispenser herein is typically one which acts upon a discrete amount ofthe odor-absorbing composition itself, typically by means of a piston ora collapsing bellows that displaces the composition through a nozzle tocreate a spray of thin liquid. Said trigger-spray dispenser typicallycomprises a pump chamber having either a piston or bellows which ismovable through a limited stroke response to the trigger for varying thevolume of said pump chamber. This pump chamber or bellows chambercollects and holds the product for dispensing. The trigger spraydispenser typically has an outlet check valve for blocking communicationand flow of fluid through the nozzle and is responsive to the pressureinside the chamber. For the piston type trigger sprayers, as the triggeris compressed, it acts on the fluid in the chamber and the spring,increasing the pressure on the fluid. For the bellows spray dispenser,as the bellows is compressed, the pressure increases on the fluid. Theincrease in fluid pressure in either trigger spray dispenser acts toopen the top outlet check valve. The top valve allows the product to beforced through the swirl chamber and out the nozzle to form a dischargepattern. An adjustable nozzle cap can be used to vary the pattern of thefluid dispensed.

For the piston spray dispenser, as the trigger is released, the springacts on the piston to return it to its original position. For thebellows spray dispenser, the bellows acts as the spring to return to itsoriginal position. This action causes a vacuum in the chamber. Theresponding fluid acts to close the outlet valve while opening the inletvalve drawing product up to the chamber from the reservoir.

A more complete disclosure of commercially available dispensing devicesappears in U.S. Pat. Nos. 4,082,223, Nozawa, issued Apr. 4, 1978;4,161,288, McKinney, issued Jul. 17, 1985; 4,434,917, Saito et al.,issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989;5,303,867, Peterson, issued Apr. 19, 1994; all of said references areincorporated herein by reference.

A broad array of trigger sprayers or finger pump sprayers are suitablefor use with the compositions of this invention. These are readilyavailable from suppliers such as Calmar, Inc., City of Industry, Calif.;CSI (Continental Sprayers, Inc.), St. Peters, Miss.; Berry PlasticsCorp., Evansville, Ind. a distributor of Guala® sprayers; or SeaquestDispensing, Cary, Ill.

The preferred trigger sprayers are the blue inserted Guala® sprayer,available from Berry Plastics Corp., or the Calmar TS800-1A sprayers,available from Calmar Inc., because of the fine uniform spraycharacteristics, spray volume, and pattern size. Any suitable bottle orcontainer can be used with the trigger sprayer, the preferred bottle isa 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape tothe Cinch® bottle. It can be made of any materials such as high densitypolyethylene, polypropylene, polyvinyl chloride, polystyrene,polyethylene terephthalate, glass, or any other material that formsbottles. Preferably, it is made of high density polyethylene or dearpolyethylene terephthalate.

For smaller four fl-oz. size (about 118 ml), a finger pump can be usedwith canister or cylindrical bottle. The preferred pump for thisapplication is the cylindrical Euromist II®, from Seaquest Dispensing.

llI. METHOD OF USE

The composition for reducing malodor impression herein can be used bydistributing, e.g., by placing the aqueous solution into a dispensingmeans, preferably a spray dispenser and spraying an effective amountonto the desired surface or article. An effective amount as definedherein means an amount sufficient to absorb odor to the point that it isnot discernible by the human sense of smell yet not so much as tosaturate or create a pool of liquid on said article or surface and sothat when dry there is no visual deposit readily discernible.Distribution can be achieved by using a spray device, a roller, a pad,etc.

Preferably, the present invention does not encompass distributing thesolution on to shiny surfaces including, e.g., chrome, glass, smoothvinyl, leather, shiny plastic, shiny wood, etc. It is preferable not todistribute the solution onto shiny surfaces because spotting and filmingcan more readily occur on the surfaces. Furthermore, the solution is notfor use on human skin, especially when an antimicrobial preservative ispresent in the composition because skin irritation can occur.

The present invention encompasses the method of spraying an effectiveamount of the composition for reducing malodor onto household surfaces.Preferably said household surfaces are selected from the groupconsisting of countertops, cabinets, walls, floors, bathroom surfacesand kitchen surfaces.

The present invention encompasses the method of spraying a mist of aneffective amount of the composition for reducing malodor onto fabricand/or fabric articles. Preferably, said fabric and/or fabric articlesinclude, but are not limited to, clothes, curtains, drapes, upholsteredfurniture, carpeting, bed linens, bath linens, tablecloths, sleepingbags, tents, car interior, e.g., car carpet, fabric car seats, etc.

The present invention encompasses the method of spraying a mist of aneffective amount of the composition for reducing malodor impression ontoand into shoes wherein said shoes are not sprayed to saturation.

The present invention encompasses the method of spraying a mist of aneffective amount of the composition for reducing malodor impression ontoshower curtains.

The present invention relates to the method of spraying a mist of aneffective amount of the composition for reducing malodor impression ontoand/or into garbage cans and/or recycling bins.

The present invention relates to the method of spraying a mist of aneffective amount of the composition for reducing malodor impression intothe air to absorb malodor.

The present invention relates to the method of spraying a mist of aneffective mount of the composition for reducing malodor impression intoand/or onto major household appliances including but not limited to:refrigerators, freezers, washing machines, automatic dryers, ovens,microwave ovens, dishwashers etc., to absorb malodor.

The present invention relates to the method of spraying a mist of aneffective amount of the composition for reducing malodor impression ontocat litter, pet bedding and pet houses to absorb malodor.

The present invention relates to the method of spraying a mist of aneffective amount of the composition for reducing malodor impression ontohousehold pets to absorb malodor.

All percentages, ratios, and parts herein, in the Specification,Examples, and Claims are by weight and are approximations unlessotherwise stated.

The following are non-limiting examples of the instant composition.Perfume compositions that are used herein are as follows:

    ______________________________________                                                             A       B       C                                        Perfume Ingredients  Wt. %   Wt. %   Wt. %                                    ______________________________________                                        3,7-Dimethyl-6-octenol                                                                             10      --      5                                        Benzyl salicylate    5       20      5                                        Benzyl acetate       10      15      5                                        Benzophenone         3       5       --                                       Octahydro-3,6,8,8-tetramethyl-1H-3A,7-                                                             2       --      --                                       methanoazulen-6-ol                                                            3-Methylene-7-methyl octan-7-ol                                                                    10      --      5                                        Dihydro-nor-cyclopentadienyl acetate                                                               5       --      5                                        1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-                                                                 10      --      --                                       hexamethyl-                                                                   cyclopenta-gamma-2-benzopyrane                                                Phenyl ethyl alcohol 15      10      20                                       3-Hydroxy-3,7-dimethyl-1,6-octadiene                                                               4       --      5                                        acetate                                                                       3-Hydroxy-3,7-dimethyl-1,6-octadiene                                                               6       15      5                                        Methyl dihydrojasmonate                                                                            3       10      5                                        2-Methyl-3(para tert butylphenyl)                                                                  10      15      20                                       propionaldehdye                                                               Phenyl ethyl acetate 2       5       1                                        4-Hydroxy-3-methoxybenzaidehyde                                                                    --      --      1                                        para-Menth-1-en-8-ol,                                                                              5       --      8                                        para-menth-1-en-1-ol                                                          Anisic aldehyde      --      --      2                                        Coumarin             --      5                                                2-Methyl-3-(para iso --      --      3                                        propylphenyl)propionaldehyde                                                  Total                100     100     100                                                           D       E                                                Perfume Material     Wt. %   Wt. %                                            ______________________________________                                        Amyl salicylate      8       --                                               Benzyl acetate       8       8                                                Benzyl Salicylate    --      2                                                Citronellol          7       27                                               Dihydromyrcenol      2       --                                               Eugenol              4       --                                               Flor acetate         8       --                                               Gulaxolide           1       --                                               Geraniol             5       --                                               Hexyl cinnamic aldehyde                                                                            2       --                                               Hydroxycitronelial   3       --                                               Lilial               2       --                                               Linalool             12      13                                               Linalyl acetate      5       --                                               Lyrat                3       --                                               Methyl dihydrojasmonate                                                                            3       --                                               Nerol                2                                                        Phenoxy ethyl propionate                                                                           --      3                                                Phenylethyl acetate  5       17                                               Phenylethyl alcohol  8       17                                               alpha-Terpineol      5       13                                               alpha-Terpinene      5       --                                               Tetrahydromyrcenol   2       --                                               Total                100     100                                              ______________________________________                                    

Perfume D is composed of about 65%, by weight, of ingredients having aClog P of about 3 or smaller.

Perfume E is composed of about 70%, by weight, of ingredients having aClog P of about 3 or smaller.

The following are non-limiting examples of the instant composition.

    ______________________________________                                                           Example I  Example II                                      Ingredients        Wt. %      Wt. %                                           ______________________________________                                        Methylated beta-cyclodextrin                                                                     0.2        --                                              Hydroxypropyl beta-cyclodextrin                                                                  --         0.2                                             Zinc chloride      1.0        1.0                                             Perfume A          0.02       --                                              Perfume B          --         0.02                                            HCl                (a)        (a)                                             Distilled water    Balance    Balance                                         ______________________________________                                         (a) To adjust solution pH to about 4.8                                   

EXAMPLES I and II

The ingredients of Examples I and II are mixed and dissolved into clearsolutions.

    ______________________________________                                                           Example III                                                                              Example IV                                      Ingredients        Wt. %      Wt. %                                           ______________________________________                                        Methylated alpha-cyclodextrin                                                                    0.1        --                                              Methylated beta-cyclodextrin                                                                     0.1        --                                              Hydroxypropyl alpha-cyclodextrin                                                                 --         0.11                                            Hydroxypropyl beta-cyclodextrin                                                                  --         0.29                                            Propylene glycol   --         0.025                                           Zinc chloride      2.0        1.0                                             Perfume C          0.03       --                                              Perfume D          --         0.02                                            HCl                (a)        (a)                                             Distilled water    Balance    Balance                                         ______________________________________                                         (a) To adjust solution pH to about 4.8                                   

Example III

The ingredients of Example III are mixed and dissolved into clearsolutions.

Example IV

The ingredients of Example IV are mixed and dissolved into clearsolutions. Hydroxypropyl alpha-cyclodextrin and hydroxypropylbeta-cyclodextrin are obtained as a mixture with an average degree ofsubstitution of about 4.9, from the hydroxypolylation reaction of amixture of alpha-cyclodextrin and beta-cyclodextrin. Propylene glycol isa minor by-product (about 6%) of the same reaction.

    ______________________________________                                                            Example V Example VI                                      Ingredients         Wt. %     Wt. %                                           ______________________________________                                        Methylated beta-cyclodextrin                                                                      0.5       --                                              Hydroxypropyl beta-cyclodextrin                                                                   --        0.6                                             Hydroxypropyl gamma-cyclodextrin                                                                  --        0.3                                             Zinc chloride       1.0       1.5                                             Perfume E           0.1       --                                              Perfume E           0.15                                                      HCl                 (a)       (a)                                             Distilled water     Balance   Balance                                         ______________________________________                                         (a) To adjust solution pH to about 4.8                                   

Examples V and VI

The ingredients of Examples V and VI are mixed and dissolved into clearsolutions. In Example VI, the hydroxypropyl beta-cyclodextrin andhydroxypropyl gamma-cyclodextrin are obtained as a mixture with anaverage degree of substitution of about 3.8, from the hydroxypolylationreaction of a mixture of beta-cyclodextrin and gamma-cyclodextrin.

    ______________________________________                                                           Example    Example                                                            VII        VIII                                            Ingredients        Wt. %      Wt. %                                           ______________________________________                                        Methylated beta-cyclodextrin                                                                     0.5        --                                              Hydroxypropyl-beta-cyclodextrin                                                                  --         0.5                                             Zinc chloride      1.0        1.0                                             Perfume E          0.1        0.1                                             Kathon CG          0.0008     0.0008                                          HCl                (a)        (a)                                             Distilled water    Balance    Balance                                         ______________________________________                                         (a) To adjust solution pH to about 4.8                                   

Examples VII and VIII

The ingredients of Examples VII and VIII are mixed and dissolved intoclear solutions.

    ______________________________________                                                             Example IX                                                                              Example X                                      Ingredients          Wt. %     Wt. %                                          ______________________________________                                        Methylated beta-cyclodextrin                                                                       0.3       --                                             Hydroxypropyl-beta-cyclodextrin                                                                    --        0.3                                            Zinc chloride        1.0       1.0                                            Perfume D            0.03      0.03                                           Kathon CG            0.0008    0.0008                                         Surfynol 465.sup.1   0.1       0.1                                            HCl                  (a)       (a)                                            Distilled water      Balance   Balance                                        ______________________________________                                         (a) To adjust solution pH to about 4.8                                        .sup.1 Surfynol 465 ® available from Air Products, has the general        structure:                                                                    ##STR1##                                                                 

Examples IX and X

The ingredients of Examples IX and X are mixed and dissolved into clearsolutions.

    ______________________________________                                                           Example    Example                                                            XI         XII                                             Ingredients        Wt. %      Wt. %                                           ______________________________________                                        Methylated beta-cyclodextrin                                                                     0.5        --                                              Hydroxypropyl beta-cyclodextrin                                                                  --         0.5                                             ZnSO.sub.4 · 7H.sub.2 O                                                                 2.2        2.2                                             Perfume D          0.03       --                                              Perfume E          --         0.04                                            Glydant Plus ® 0.01       0.01                                            Distilled Water    Balance    Balance                                         ______________________________________                                    

Example XI and XII

The ingredients of Example XI and XII are mixed and dissolved into clearsolutions.

Examples XIII

The composition of Example IV is sprayed onto clothing using a blueinserted Guala® trigger sprayer, available from Berry Plastics Corp. andallowed to evaporate off of the clothing.

Example XIV

The composition of Example VII is sprayed onto a kitchen countertopusing blue inserted Guala® trigger sprayer, available from BerryPlastics Corp., and wiped off with a paper towel.

Example XV

The composition of Example X is sprayed onto clothes using a cylindricalEuromist II® pump sprayer available from Seaquest Dispensing, andallowed to evaporate off of the clothing.

What is claimed:
 1. An article of manufacture, which comprises:A. anaqueous composition for reducing malodor impression, comprising:i. fromabout 0.01% to about 0.5%, by weight of the composition, of perfume; ii.from about 0.1% to about 5%, by weight of the composition, of methylatedbeta-cyclodextrin wherein the weight ratio of perfume to cyclodextrin isfrom about 4:100 to about 50:100; iii. from about 0.1% to about 10%, byweight of the composition, of solubilized, water-soluble zinc salt; iv.from about 0.05% to about 1%, by weight of the composition, oflow-foaming surfactant; and v. water; andB. a trigger spray dispenserwherein the container is transparent polyethyleneterephthalate;andwherein said composition is essentially free of any material thatwould soil or stain fabric wherein said composition contains less thanabout 1%, by weight of the composition, of low molecular weightmonohydric alcohols and has a pH of from about 4 to about
 5. 2. Anarticle of manufacture, which comprises:A. an aqueous composition forreducing malodor impression, for use on inanimate surfaces,comprising:i. from about 0.015% to about 0.3%, by weight of thecomposition of perfume wherein at least 25% of the perfume ingredientshave a Clog P of 3 or smaller; ii. from about 0.1% to about 5%, byweight of the composition, of hydroxypropyl beta-cyclodextrin, whereinthe perfume to cyclodextrin weight ratio is from about 5:100 to about25:100; iii. from about 0.3% to about 5%, by weight of the composition,of ZnCl₂ ; iv. from about 0.05% to about 1%, by weight of thecomposition, of low-foaming surfactant; v. from about 0.0001% to about0.01%, by weight of the composition, of solubilized, water-soluble,antimicrobial preservative comprising a mixture of5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one; and vi. water; and B. a pump spraydispenser wherein the container is transparentpolyethyleneterephthalate; andwherein said composition is essentiallyfree of any material that would soil or stain fabric and wherein saidcomposition contains less than about 3%, by weight of the composition,of low molecular weight monohydric alcohols and has a pH of from about 4to about
 5. 3. An article of manufacture, which comprises:A. an aqueouscomposition for reducing malodor impression, comprising:i. from about0.01% to about 0.5%, by weight of the composition, of perfume; ii. fromabout 0.1% to about 5%, by weight of the composition, of a mixture ofhydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrinwherein the weight ratio of perfume to cyclodextrin is from about 3:100to about 100:100; iii. from about 0.1% to about 10%, by weight of thecomposition, of ZnCl₂ ; iv. from about 0.05% to about 1%, by weight ofthe composition, of low-forming surfactant; and v. water; andB. atrigger-spray dispenser wherein the container is transparentpolyethyleneterephthalate; andwherein said composition is essentiallyfree of any material that would soil or stain fabric and wherein saidcomposition contains less than about 3%, by weight of the composition,of low molecular weight monohydric alcohols and has a pH of from about 4to about 5.